Method for controlling pests in soybean

ABSTRACT

A method for controlling pests of soybean plants comprises the step of contacting the soybean plant, parts of it, its propagation material, the pests, their food supply, habitat or breeding grounds with one or more components of the ginkgo tree selected from the group consisting of bilobalide, ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J and ginkgolide M.

This application is a National Stage application of InternationalApplication No. PCT/EP2015/053872, filed Feb. 25, 2015, which claims thebenefit of U.S. Provisional Application No. 61/945,149, filed Feb. 27,2014. This application also claims priority under 35 U.S.C. §119 toEuropean Patent Application No. 14158379.9, filed Mar. 7, 2014.

The invention relates to methods of pest control by insecticidalcomponents of the ginkgo tree.

Faboideae, such as soybeans (Glycine max) and lima beans (Phaseoluslunatus), are important commercial crops.

Soybeans are considered to be a source of complete protein (Henkel, J.,2000, “Soy: Health Claims for Soy Protein, Question About OtherComponents”. FDA Consumer (Food and Drug Administration 34 (3): 18-20).For this reason, soy is a good source of protein. According to the USFood and Drug Administration, soy protein products can be goodsubstitutes for animal products because soy offers a ‘complete’ proteinprofile. Soy protein products can replace animal-based foods which alsohave complete proteins but tend to contain more fat, especiallysaturated fat without requiring major adjustments elsewhere in the diet.

Soybean protein isolate is highly valuable as it has a biological valueof 74 (Protein Quality Evaluation: Report of the Joint FAO/WHO ExpertConsultation. Bethesda, Md. (USA): Food and Agriculture Organization ofthe United Nations (Food and Nutrition Paper No. 51). December 1989).

In agriculture soybeans can produce at least twice as much protein peracre than some other major vegetable or grain crop, e.g. 5 to 10 timesmore protein per acre than land set aside for grazing animals to makemilk, and up to 15 times more protein per acre than land set aside formeat production (“Soy Benefits”, National Soybean Research Laboratory,February 2012).

Thus, soybeans can be regarded as a globally important crop providingoil and protein.

Nevertheless, soybean plants are vulnerable to a wide range of bacterialdiseases, fungal diseases, viral diseases and parasites. Soybeans areconsidered to be e.g. the secondmost valuable agricultural export in theUnited States behind corn.

Consequently, in view of the importance of soybean in agriculture,proper pest management is required in order not to jeopardize yield andquality of the soybean crops.

Stink bugs (order of Hemiptera, family of Pentatomidae) are animal pestsand true bugs. They are probably one of the most common pest problems insoybean (Stewart et al., Soybean Insects—Stink bugs, University ofTennessee Institute of Agriculture, W200 09-0098).

Stink bugs feed on over 52 plants, including native and ornamentaltrees, shrubs, vines, weeds, and many cultivated crops such as corn andcotton, as well as numerous uncultivated plants, and their preferredhosts are nearly all wild plants. They build up on these hosts and moveto soybeans late in the season as their preferred foods mature.

Stink bugs may feed on many parts of the plant; however, they typicallytarget developing seed including the pods, meaning that injury tosoybean seed is the primary problem associated with stink buginfestations.

Brown or blackish spots may occur where their mouthparts penetrate theplant tissue, but little external signs of feeding injury may bepresent. Feeding may cause deformation, shriveling or abortion of smallseed. Larger seed may only be partly discolored by feeding injury, butthis can affect seed quality. High levels of seed abortion may cause the“green bean effect” where foliage is retained and plant maturity isdelayed (Stewart et al., Soybean Insects—Stink bugs, University ofTennessee Institute of Agriculture, W200 09-0098).

Stink bugs inflict mechanical injury to the seed as well as transmittingthe yeast-spot disease organism. The degree of damage caused by thispest depends to some extent on the developmental stage of the seed whenit is pierced by the stink bug's needlelike mouthparts. The younger theseed when damaged, the greater the yield reduction. Although late seasoninfestations may not affect yield, bean oil content and germination willbe reduced.

In certain regions the green stink bug (Acrosternum hilare) is one ofthe most common species that feeds on soybean. The brown stink bug(Euschistus servus) is another common component of the stink bugcomplex.

Of the complex of sucking bugs that occur in cultivation, the brownstinkbug Euschistus heros is currently considered to be the mostabundant species in northern Parana to Central Brazil (Correa-Ferreira &Panizzi, 1999), and is a significant problem in soybean (Schmidt et al.,2003). The bugs occur in soybeans from the vegetative stage and areharmful from the beginning of pod formation until grain maturity. Theycause damage to the seed (Galileo & Heinrichs 1978, Panizzi & SlanskyJr., 15, 1985) and can also open the way to fungal diseases and causephysiological disorders, such as soybean leaf retention (Galileo &Heinrichs 1978, Todd & Herzog, 1980).

Other plant feeding species that may be present include thered-shouldered stink bug (Thyanta custator) and the dusky-brown stinkbug (Euschistus tristigmus). Another species, the southern green stinkbug (Nezara viridula), is often confined to the southernmost counties ofthe US. Predatory (beneficial) stink bugs such as the spined soldier bug(Podisus Maculaventris) may also be found in soybean and are sometimesmistaken for brown or dusky-brown stink bugs.

Control of stinkbugs in soybean is often vital to prevent significanteconomic damage.

Insecticides commonly used to control stinkbugs include pyrethroids,neonicotinoids and organophosphates, though pyrethroid insecticides areusually the method of choice for controlling stink bugs in soybean.However, there are increasing problems with insecticide resistance,particularly in brown stink bug populations and particularly topyrethroids. Euschistus heros can also be difficult to manage usingorganophosphates or endosulfan (Sosa-Gomez et al., 2009). There istherefore a need for effective ecological methods of controllingstinkbugs in soybean.

Particularly insecticides acting on the gamma-aminobutyric acid(GABA)-gated chloride channel (disclosed in e.g. WO 2005/085216 (EP 1731 512), WO 2009/002809 and WO 2009/080250) seem to be effective forcontrolling stinkbugs, especially in soybean such as described inWO2012/104331.

It has now been found that specific natural components of the ginkgotree provide an efficient control against pests on Faboideae, inparticular soybeans, especially against pests from the families ofPentatomidae and Thripidae.

These compounds therefore represent an important solution forcontrolling pests of Faboideae, in particular soybeans, in particularpests from the family of pentatomidae, stink bugs, and therebysafeguarding plants, crops and propagation material from the infestationby such pests, particularly where the pests are resistant to currentmethods.

An acaricidal activity of ginkgolide C is disclosed in CN 102379296 (A).WO 2005/025587 discloses an insecticidal activity of mixtures ofginkgolide A, B and bilobalide against two spotted spider mites andgreen peach aphid. WO 2004/034853 discloses insecticidal mixtures ofbilobalide, ginkgolide A, B or C and unspecified derivatives thereofwith organophosphates and pyrethroids against rice pests.

None of these documents discloses an acceptable efficacy of bilobalideor ginkgolides against typical pests of Faboideae, preferably soybeans,in particular stink bugs. As stated above, these pests are difficult tocontrol with typical soybean pesticides.

Accordingly, in one aspect of the invention there is provided a methodfor controlling pests of Faboideae, in particular soybean plants,comprising the step of contacting the Faboideae, in particular soybean,plant, parts of it, its propagation material, the pests, their foodsupply, habitat or breeding grounds with one or more components of theginkgo tree selected from the group consisting of bilobalide, ginkgolideA, ginkgolide B, ginkgolide C, ginkgolide J and ginkgolide M.

In a further aspect of the invention there is provided the use of one ormore components of the ginkgo tree selected from the group consisting ofbilobalide, ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J andginkgolide M for controlling pests in Faboideae, in particular soybeancrops.

In a further aspect of the invention there is provided a method forcontrolling pests from the family of Pentatomidae and/or Thripidae,comprising the step of contacting the pests, their food supply habitatand/or breeding ground with one or more components of the ginkgo treeselected from the group consisting of bilobalide, ginkgolide A,ginkgolide B, ginkgolide C, ginkgolide J and ginkgolide M.

In yet a further aspect of the invention there is provided the use ofone or more components of the ginkgo tree selected from the groupconsisting of bilobalide, ginkgolide A, ginkgolide B, ginkgolide C,ginkgolide J and ginkgolide M for controlling pests from the family ofPentatomidae and/or Thripidae.

Bilobalide and the ginkgolides are known components of the ginkgo treehaving the following structures:

a) Bilobalide:

Bilobalide is the common name for(3aS,5aR,8aS,9R,10aR)-9-tert-butyl-8,9-dihydroxydihydro-9H-furo[2,3-b]furo[3′,2′;2,3]cyclopenta[1,2-c]furan-2,4,7(3H,8H)-trione(CAS 33570-04-6).

b) Ginkgolides:

Ginkgolide R¹ R² R³ CAS Ginkgolide A —H —OH —H 15291-75-5 Ginkgolide B—H —OH —OH 15291-77-7 Ginkgolide C —OH —OH —OH 15291-76-6 Ginkgolide J—OH —OH —H 15291-79-9 Ginkgolide M —OH —H —OH 15291-78-8

The above compounds can be used in pure form, as mixtures or in the formof extracts of ginkgo leaves, which may be enriched with the abovecompounds to a certain degree.

The compounds are commercially available, or can be obtained, preferablyfrom ginkgo leaves by methods known in the art and described e.g. inU.S. Pat. No. 5,700,468, EP-A 360 556, EP-A 0 431 535 and JP-A09-110713.

Further, the compounds bilobalide (in enantiopure form), ginkgolide A(in its racemic form) and ginkgolide B (in its racemic form) can beobtained by chemical synthesis, as disclosed e.g. in Tetrahedron Letters(1988), 29(28), 3423-6, Tetrahedron Letters (1988), 29(26), 3205-6 andJournal of the American Chemical Society (2000), 122(35), 8453-8463,respectively.

The methods and uses of the invention are for controlling and/orpreventing infestation of Faboideae plants, Faboideae crops andFaboideae propagation material by pests. In one preferred embodiment,the Faboideae plants, crops or propagation material are soybean plants,crops or propagation material. In another preferred embodiment, theFaboideae plants, crops or propagation material are lima bean plants,crops or propagation material. In general the pests are from the familyof Pentatomidae and/or Thripidae. Preferably the methods and uses of thepresent invention are applied against pests from the family ofPentatomidae, stink bugs. More preferably against stink bugs that areresistant to other insecticides, e.g. pyrethroid insecticides. Stinkbugsthat are “resistant” to a particular insecticide refers e.g. to strainsof stinkbugs that are less sensitive to that insecticide compared to theexpected sensitivity of the same species of stinkbug. The expectedsensitivity can be measured using e.g. a strain that has not previouslybeen exposed to the insecticide.

In one aspect of the present invention, the method comprises applying toFaboideae plants, crops and/or propagation material, in particularsoybean plants, soybean crops and/or propagation material of soybeanplants or lima bean plants, lima bean crop and/or propagation materialof lima bean plants, a compound of the invention, wherein the method isfor controlling and/or preventing infestation by pests.

Especially the method is for controlling and/or preventing infestationby pests from the family of Pentatomidae and/or Thripidae (such asDichromothrips like Dichromothrips corbetti), in particular from thefamily of Pentatomidae, stink bugs; even more particular for controllingand/or preventing infestation by Acrosternum spp., Euschistus spp.,Nezara spp. and/or Piezodrus spp., most particularly by Acrosternumhilare, Euschistus heros, Nezara viridula and/or Piezodrus guildini, andespecially by Euschistus heros. Further Pentatomidae pests that can becontrolled according to the invention are Eysarcoris, in particularEysarcoris aeneus (forest shield bug). Further Heteroptera pests thatcan be controlled according to the invention include Miridae, such asTrigonotylus like Trigonotylus caelestialium (rice leaf bug).

A further aspect the invention provides the use of the compounds of theinvention for the general control of pests from the family ofPentatomidae (stink bugs) and/or Thripidae, preferably for the controlof pests from the family of Pentatomidae, in particular for the controtof Acrosternum spp., Euschistus spp., Nezara spp. and/or Piezodrus spp.,more preferably for the control of Acrosternum hilare, Euschistus heros,Nezara viridula and/or Piezodrus guildini, and most preferably for thecontrol of Euschistus heros.

In another aspect, the present invention provides the use of thecompounds of the invention for controlling pests that are resistant toone or more other insecticides, preferably pyrethroids, neonicotinoidsand organophosphates, and more preferably pyrethroid insecticides.

Preferably the compounds of the invention are used for controlling pestsfrom the family of Pentatomidae, stinkbugs, that are resistant to one ormore other insecticides, preferably pyrethroids, neonicotinoids andorganophosphates, and more preferably pyrethroid insecticides, inparticular for the control of Acrosternum spp., Euschistus spp., Nezaraspp. and/or Piezodrus spp., preferably for the control of Acrosternumhilare, Euschistus heros, Nezara viridula and/or Piezodrus guildini, andmost preferably for the control of Euschistus heros that are resistantto one or more other insecticides, preferably pyrethroids,neonicotinoids and organophosphates, and more preferably pyrethroidinsecticides.

The compounds of the invention are bilobalide, ginkgolide A, ginkgolideB, ginkgolide C, ginkgolide J and ginkgolide M or mixtures of one ormore of these compounds. Preferred are bilobalide and/or ginkgolide A.

Pests

The compounds applied in the methods of the invention may be used onFaboideae, in particular soybean or lima beans, to control, for example:

Elasmopalpus lignosellus, Diloboderus abderus, Diabrotica speciosa,Sternechus subsignatus, Formicidae, Agrotis ypsilon, Julus ssp.,Anticarsia gemmatalis, Megacopta spp., Megascelis ssp., Procornitermesssp., Gryllotalpidae, Nezara viridula, Piezodorus spp., Acrosternumspp., Neomegalotomus spp., Cerotoma trifurcata, Popillia japonica,Edessa spp., Liogenys fuscus, Euchistus heros, stem borer, Dectes spp.,stalk borer, Scaptocoris castanea, phyllophaga spp., Pseudoplusiaincludens, Spodoptera spp., Bemisia tabaci, Agriotes spp., Thripidae,preferably Diloboderus abderus, Diabrotica speciosa, Nezara viridula,Piezodorus spp., Acrosternum spp., Cerotoma trifurcata, Popilliajaponica, Euchistus heros, phyllophaga spp., Agriotes spp., and Dectestexanus.

The compounds of the invention are preferably used on Faboideae, inparticular soybean or lima beans, to control stinkbugs, e.g. Nezara spp.(e.g. Nezara viridula, Nezara antennata, Nezara hilaris), Piezodorusspp. (e.g. Piezodorus guildinii), Acrosternum spp. (e.g. Acrosternumhilare), Euchistus spp. (e.g. Euchistus heros, Euschistus servus),Halyomorpha halys, Megacopta cribaria, Plautia crossota, Riptortusclavatus, Rhopalus msculatus, Antestiopsis orbitalus, Dectes texanus,Dichelops spp. (e.g. Dichelops furcatus, Dichelops Melacanthus),Eurygaster spp. (e.g. Eurygaster intergriceps, Eurygaster maurd),Oebalus spp. (e.g. Oebalus mexicana, Oebalus poecilus, Oebalus pugnase,Scotinophara spp. (e.g. Scotinophara lurida, Scotinophara coarctatd).Preferred targets include Acrosternum hilare, Antestiopsis orbitalus,Dichelops furcatus, Dichelops melacanthus, Euchistus heros, Euschistusservus, Megacopta cribaria, Nezara viridula, Nezara hilare, Piezodorusguildinii, Halyomorpha halys. In one embodiment the stinkbug target isNezara viridula, Piezodorus spp., Acrosternum spp., Euchistus heros.Euschistus and in particular Euchistus heros are the preferred targets.

Further Pentatomidae pests that can be controlled according to theinvention are Eysarcoris, in particular Eysarcoris aeneus.

Applications

Application of the compounds of the invention is preferably to a crop ofFaboideae, such as soybean or lima bean plants, the locus thereof orpropagation material thereof. Preferably application is to a crop ofFaboideae, such as soybean or lima bean plants or the locus thereof,more preferably to a crop of soybean plants. Application may be beforeinfestation or when the pest is present. Application of the compounds ofthe invention can be performed according to any of the usual modes ofapplication, e.g. foliar, drench, soil, in furrow etc. Control ofstinkbugs can be achieved by foliar application, which is a preferredmode of application according to the invention.

In another preferred embodiment, the compounds of the invention areapplied to Faboideae crops by soil-drench application. In one preferredembodiment, the Faboideae crops are soybean crops. In another preferredembodiment the Faboideae crops are lima bean crops.

In a further preferred embodiment the compounds of the invention areapplied as seed-treatment to seeds of Faboideae crops. In one preferredembodiment, the Faboideae crops are soybean crops. In another preferredembodiment the Faboideae crops are lima bean crops.

The pest, e.g. the stink bugs, the plant, soil or water in which theplant is growing can be contacted with the compounds of the invention orcomposition(s) containing them by any further application method knownin the art. As such, “contacting” includes both direct contact (applyingthe compounds/compositions directly on the animal pest orplant—typically to the foliage, stem or roots of the plant) and indirectcontact (applying the compounds/compositions to the locus of the animalpest or plant).

The compounds of the invention or the pesticidal compositions comprisingthem may be used to protect growing plants and crops from attack orinfestation by animal pests, especially from stink bugs, in particularfrom Euschistus, more particularly from E. heros, by contacting theplant/crop with a pesticidally effective amount of compounds of theinvention. The term “crop” refers both to growing and harvested crops.

The compounds of the invention may be applied in combination with anattractant. An attractant is a chemical that causes the insect tomigrate towards the location of application. For control of stinkbugs itcan be advantageous to apply the compounds of the invention with anattractant, particularly when the application is foliar. Stinkbugs areoften located near to the ground, and application of an attractant mayencourage migration up the plant towards the active ingredient.

Suitable attractants include glucose, sacchrose, salt, glutamate, citricacid, soybean oil, peanut oil and soybean milk. Glutamate and citricacid are of particular interest, with citric acid being preferred.

An attractant may be premixed with the compound of the invention priorto application, e.g. as a readymix or tankmix, or by simultaneousapplication or sequential application to the plant. Suitable rates ofattractants are for example 0.02 kg/ha-3 kg/ha.

The compounds of the invention are preferably used for pest control onFaboideae, in particular soybean or lima beans, at 1-500 g/ha,preferably 10-100 g/ha.

The compounds of the invention are suitable for use on any Faboideaeplant, such as soybean plants or lima bean plants, including those thathave been genetically modified to be resistant to active ingredientssuch as herbicides or to produce biologically active compounds thatcontrol infestation by plant pests.

In a further preferred embodiment, transgenic plants and plant cultivarsobtained by genetic engineering methods, if appropriate in combinationwith conventional methods (Genetically Modified Organisms), and partsthereof, are treated. Particularly preferably, plants of the plantcultivars which are in each case commercially available or in use aretreated according to the invention. Plant cultivars are understood asmeaning plants having novel properties (“traits”) which have beenobtained by conventional breeding, by mutagenesis or by recombinant DNAtechniques.

These can be cultivars, bio- or genotypes. Depending on the plantspecies or plant cultivars, their location and growth conditions (soils,climate, vegetation period, diet), the treatment according to theinvention may also result in superadditive “synergistic”) effects.

Thus, for example, reduced application rates and/or a widening of theactivity spectrum and/or an increase in the activity of the substancesand compositions which can be used according to the invention, betterplant growth, increased tolerance to high or low temperatures, increasedtolerance to drought or to water or soil salt content, increasedflowering performance, easier harvesting, accelerated maturation, higherharvest yields, higher quality and/or a higher nutritional value of theharvested products, better storage stability and/or processability ofthe harvested products are possible, which exceed the effects which wereactually to be expected.

The preferred transgenic plants or plant cultivars (obtained by geneticengineering) which are to be treated according to the invention includeall plants which, by virtue of the genetic modification, receivedgenetic material which imparts particularly advantageous, useful traitsto these plants.

Examples of such traits are better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, higher quality and/or ahigher nutritional value of the harvested products, better storagestability and/or processability of the harvested products.

Further and particularly emphasized examples of such traits are a betterdefense of the plants against animal and microbial pests, such asagainst insects, mites, phytopathogenic fungi, bacteria and/or viruses,and also increased tolerance of the plants to certain herbicidallyactive compounds.

Traits that are emphasized in particular are the increased defense ofthe plants against insects, arachnids, nematodes and slugs and snails byvirtue of toxins formed in the plants, in particular those formed in theplants by the genetic material from Bacillus thuringiensis (for exampleby the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2,Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (referredto herein as “Bt plants”). Traits that are also particularly emphasizedare the increased defense of the plants against fungi, bacteria andviruses by systemic acquired resistance (SAR), systemin, phytoalexins,elicitors and resistance genes and correspondingly expressed proteinsand toxins.

Traits that are furthermore particularly emphasized are the increasedtolerance of the plants to certain herbicidally active compounds, forexample imidazolinones, sulphonylureas, glyphosate or phosphinotricin(for example the “PAT” gene). The genes which impart the desired traitsin question can also be present in combination with one another in thetransgenic plants.

Examples of “Bt plants” are soybean varieties which are sold under thetrade names YIELD GARD(®).

Examples of herbicide-tolerant plants which may be mentioned are soyabean varieties which are sold under the trade names Roundup Ready(®)(tolerance to glyphosate), Liberty Link(®) (tolerance tophosphinotricin), IMI(®) (tolerance to imidazolinones) and STS(®)(tolerance to sulphonylureas).

Herbicide-resistant plants (plants bred in a conventional manner forherbicide tolerance) which may be mentioned include the varieties soldunder the name Clearfield(®) (for example maize).

Of particular interest are Faboideae, in particular soybean plants,carrying two or more traits (e.g. Enlist®), glyphosate (e.g. RoundupReady®, Roundup Ready 2 Yield®), sulfonylurea (e.g. STS®), glufosinate(e.g. Liberty Link®, Ignite®), Dicamba (Monsanto) HPPD tolerance (e.g.isoxaflutole herbicide) (Bayer CropScience, Syngenta). Double or triplestack in soybean plants of any of the traits described here are also ofinterest, including glyphosate and sulfonyl-urea tolerance (e.g. OptimumGAT®, plants stacked with STS® and Roundup Ready® or Roundup Ready 2Yield®), dicamba and glyphosate tolerance (Monsanto). Soybean CystNematode resistance soybean (SCN®-Syngenta) and soybean with Aphidresistant trait (AMT®-Syngneta) are also of interest.

These statements also apply to plant cultivars having these genetictraits or genetic traits still to be developed, which plant cultivarswill be developed and/or marketed in the future.

Mixtures

The compounds of the invention may be applied in the methods of thepresent invention in mixtures with fertilizers (for example nitrogen-,potassium- or phosphorus-containing fertilizers). Suitable formulationtypes include granules of fertilizer. The mixtures preferably contain upto 25% by weight of the compound of the invention.

The compositions of this invention may contain other compounds havingbiological activity, for example micronutrients or compounds havingfungicidal activity or which possess plant growth regulating,herbicidal, insecticidal, nematicidal or acaricidal activity.

The compounds applied in the methods of the present invention may be thesole active ingredient of the composition or it may be admixed with oneor more additional active ingredients such as a pesticide, fungicide,synergist, herbicide or plant growth regulator where appropriate. Anadditional active ingredient may: provide a composition having a broaderspectrum of activity or increased persistence at a locus; synergize theactivity or complement the activity (for example by increasing the speedof effect or overcoming repellency) of the compound of the invention; orhelp to overcome or prevent the development of resistance to individualcomponents. The particular additional active ingredient will depend uponthe intended utility of the composition.

According to one embodiment of the present invention, individualcomponents of the composition according to the invention such as partsof a kit or parts of a binary or ternary mixture may be mixed by theuser himself in a spray tank and further auxiliaries may be added, ifappropriate.

The compounds of the invention may be mixed with soil, peat or otherrooting media for the protection of plants against seed-borne,soil-borne or foliar fungal diseases.

Examples of suitable synergists for use in the compositions includepiperonyl butoxide, sesamex, safroxan and dodecyl imidazole.

Suitable herbicides and plant-growth regulators for inclusion in thecompositions will depend upon the intended target and the effectrequired.

An example of a rice selective herbicide which may be included ispropanil. An example of a plant growth regulator for use in cotton isPIX™.

Formulations

The invention also relates to agrochemical compositions comprising oneor more auxiliary agents and at least one compound of the inventionand/or one of its individual embodiments, which are applied in themethods of the present invention.

An agrochemical composition comprises a pesticidally effective amount ofa compound of the invention and/or one of its individual embodiments.The term “effective amount” denotes an amount of the composition or ofthe compounds of the invention, which is sufficient for controllinganimal pests on cultivated plants or in the protection of materials andwhich does not result in a substantial damage to the treated plants.Such an amount can vary in a broad range and is dependent on variousfactors, such as the pest species to be controlled, the treatedcultivated plant or material, the climatic conditions and the specificcompound used.

The compounds of the invention can be converted into customary types ofagrochemical compositions, e.g. solutions, emulsions, suspensions,dusts, powders, pastes, granules, pressings, capsules, and mixturesthereof. Examples for composition types are suspensions (e.g. SC, OD,FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES,ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders ordusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules(e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as wellas gel formulations for the treatment of plant propagation materialssuch as seeds (e.g. GF). These and further compositions types aredefined in the “Catalogue of pesticide formulation types andinternational coding system”, Technical Monograph No. 2, 6th Ed. May2008, CropLife International.

The compositions are prepared in a known manner, such as described byMollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001;or Knowles, New developments in crop protection product formulation,Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers orfillers, surfactants, dispersants, emulsifiers, wetters, adjuvants,solubilizers, penetration enhancers, protective colloids, adhesionagents, thickeners, humectants, repellents, attractants, feedingstimulants, compatibilizers, bactericides, anti-freezing agents,anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents,such as mineral oil fractions of medium to high boiling point, e.g.kerosene, diesel oil; oils of vegetable or animal origin; aliphatic,cyclic and aromatic hydrocarbons, e.g. toluene, paraffin,tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol,propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones,e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acidesters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides,e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixturesthereof.

Suitable solid carriers or fillers are mineral earths, e.g. silicates,silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite,diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate,magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers,e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas;products of vegetable origin, e.g. cereal meal, tree bark meal, woodmeal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic,cationic, nonionic and amphoteric surfactants, block polymers,polyelectrolytes, and mixtures thereof. Such surfactants can be used asemulsifier, dispersant, solubilizer, wetter, penetration enhancer,protective colloid, or adjuvant. Examples of surfactants are listed inMcCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon'sDirectories, Glen Rock, USA, 2008 (International Ed. or North AmericanEd.).

Suitable anionic surfactants are alkali, alkaline earth or ammoniumsalts of sulfonates, sulfates, phosphates, carboxylates, and mixturesthereof. Examples of sulfonates are alkylaryl sulfonates,diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates,sulfonates of fatty acids and oils, sulfonates of ethoxylatedalkylphenols, sulfonates of alkoxylated arylphenols, sulfonates ofcondensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes,sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates orsulfosuccinamates. Examples of sulfates are sulfates of fatty acids andoils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols,or of fatty acid esters. Examples of phosphates are phosphate esters.Examples of carboxylates are alkyl carboxylates, and carboxylatedalcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-substituted fatty acidamides, amine oxides, esters, sugar-based surfactants, polymericsurfactants, and mixtures thereof. Examples of alkoxylates are compoundssuch as alcohols, alkylphenols, amines, amides, arylphenols, fatty acidsor fatty acid esters which have been alkoxylated with 1 to 50equivalents. Ethylene oxide and/or propylene oxide may be employed forthe alkoxylation, preferably ethylene oxide. Examples of N-substitutedfatty acid amides are fatty acid glucamides or fatty acid alkanolamides.Examples of esters are fatty acid esters, glycerol esters ormonoglycerides. Examples of sugar-based surfactants are sorbitans,ethoxylated sorbitans, sucrose and glucose esters oralkylpolyglucosides. Examples of polymeric surfactants are home- orcopolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for examplequaternary ammonium compounds with one or two hydrophobic groups, orsalts of long-chain primary amines. Suitable amphoteric surfactants arealkylbetains and imidazolines. Suitable block polymers are blockpolymers of the A-B or A-B-A type comprising blocks of polyethyleneoxide and polypropylene oxide, or of the A-B-C type comprising alkanol,polyethylene oxide and polypropylene oxide. Suitable polyelectrolytesare polyacids or polybases. Examples of polyacids are alkali salts ofpolyacrylic acid or polyacid comb polymers. Examples of polybases arepolyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even nopesticidal activity themselves, and which improve the biologicalperformance of the compound of formula (I) on the target. Examples aresurfactants, mineral or vegetable oils, and other auxilaries. Furtherexamples are listed by Knowles, Adjuvants and additives, Agrow ReportsDS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum,carboxymethylcellulose), anorganic clays (organically modified orunmodified), polycarboxylates, and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives suchas alkylisothiazolinones and benzisothiazolinones.

Suitable anti-freezing agents are ethylene glycol, propylene glycol,urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, andsalts of fatty acids.

Suitable colorants (e.g. in red, blue, or green) are pigments of lowwater solubility and water-soluble dyes. Examples are inorganiccolorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) andorganic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).

Suitable tackifiers or binders are polyvinylpyrrolidons,polyvinylacetates, polyvinyl alcohols, polyacrylates, biological orsynthetic waxes, and cellulose ethers.

Agrochemical compositions containing one or more components of theginkgo tree according to the invention generally comprise between 0.01and 95%, preferably between 0.1 and 90%, and in particular between 0.5and 75%, by weight of active substance. The active substances areemployed in a purity of from 90% to 100%, preferably from 95% to 100%(according to NMR spectrum).

Solutions for seed treatment (LS), suspoemulsions (SE), flowableconcentrates (FS), powders for dry treatment (DS), water-dispersiblepowders for slurry treatment (WS), water-soluble powders (SS), emulsions(ES), emulsifiable concentrates (EC) and gels (GF) are usually employedfor the purposes of treatment of plant propagation materials,particularly seeds. The compositions in question give, aftertwo-to-tenfold dilution, active substance concentrations of from 0.01 to60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-usepreparations. Application can be carried out before or during sowing.Methods for applying compound of formula (I) and compositions thereof,respectively, on to plant propagation material, especially seeds includedressing, coating, pelleting, dusting, soaking and in-furrow applicationmethods of the propagation material. Preferably, compound of formula (I)or the compositions thereof, respectively, are applied on to the plantpropagation material by a method such that germination is not induced,e. g. by seed dressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of active substancesapplied are, depending on the kind of effect desired, from 0.001 to 2 kgper ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha. Inanother embodiment the amount is from 0.001 to 0.500 kg/ha, inparticular 0.01 to 0.1 kg/ha.

In treatment of plant propagation materials such as seeds, e. g. bydusting, coating or drenching seed, amounts of active substance of from0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to100 g and most preferably from 5 to 100 g, per 100 kilogram of plantpropagation material (preferably seeds) are generally required.

When used in the protection of materials or stored products, the amountof active substance applied depends on the kind of application area andon the desired effect. Amounts customarily applied in the protection ofmaterials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of activesubstance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, ormicronutrients, and further pesticides (e.g. herbicides, insecticides,fungicides, growth regulators, safeners) may be added to the activesubstances or the compositions comprising them as premix or, ifappropriate not until immediately prior to use (tank mix). These agentscan be admixed with the compositions according to the invention in aweight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user applies the composition according to the invention usually froma predosage device, a knapsack sprayer, a spray tank, a spray plane, oran irrigation system. Usually, the agrochemical composition is made upwith water, buffer, and/or further auxiliaries to the desiredapplication concentration and the ready-to-use spray liquor or theagrochemical composition according to the invention is thus obtained.Usually, 20 to 2000 liters, preferably 50 to 400 liters, of theready-to-use spray liquor are applied per hectare of agricultural usefularea.

According to one embodiment, individual components of the compositionaccording to the invention such as parts of a kit or parts of a binaryor ternary mixture may be mixed by the user himself in a spray tank andfurther auxiliaries may be added, if appropriate.

In a further embodiment, either individual components of the compositionaccording to the invention or partially premixed components, e. g.components comprising compounds of the invention (or one of itsindividual embodiments) and/or future active substances may be mixed bythe user in a spray tank and further auxiliaries and additives may beadded, if appropriate.

In a further embodiment, either individual components of the compositionaccording to the invention or partially premixed components can beapplied jointly (e.g. after tank mix) or consecutively.

EXAMPLES

The present invention is now illustrated in further details by thefollowing examples, without imposing any limitation thereto.

A. Compounds

Bilobalide, ginkgolide A, ginkgolide B, ginkgolide C and ginkgolide Jare commercially available (e.g. from Interchim) and were purchased fromcommercial sources.

B. Biology

The biological activity and effectivity of the compounds applied in themethods of the invention can be evaluated e.g. in the following assays.

B.1 Green Soldier Stink Bug (Nezara viridula)

The active compound is dissolved at the desired concentration in amixture of 1:1 (vol:vol) distilled water:acetone. Surfactant (KineticHV) is added at a rate of 0.01% (vol/vol).The test solution is preparedat the day of use.

Soybean pods were placed in microwavable plastic cups lined with moistfilter paper and inoculated with ten 3rd instar N. viridula. Using ahand atomizer, approximately 2 ml solution is sprayed into each cup.Treated cups were kept at about 28-29° C. and relative humidity of about50-60%. Percent mortality was recorded after 5 days.

In this test, bilobalide, ginkgolide A and ginkgolide B at 500 ppmshowed at least 75% mortality in comparison with untreated controls.

In this test, bilobalide, and ginkgolide A at 300 ppm showed at least75% mortality in comparison with untreated controls.

In this test, bilobalide, and ginkgolide A at 100 ppm showed at least75% mortality in comparison with untreated controls.

In this test, bilobalide, and ginkgolide A at 10 ppm showed at least 75%mortality in comparison with untreated controls.

B.2 Orchid Thrips (Dichromothrips corbetti)

Dichromothrips corbetti adults used for bioassay were obtained from acolony maintained continuously under laboratory conditions. For testingpurposes, the test compound is diluted in a 1:1 mixture of acetone:water(vol:vol), plus Kinetic HV at a rate of 0.01% v/v.

Thrips potency of each compound was evaluated by using afloral-immersion technique. All petals of individual, intact orchidflowers were dipped into treatment solution and allowed to dry in Petridishes. Treated petals were placed into individual re-sealable plasticalong with about 20 adult thrips. All test arenas were held undercontinuous light and a temperature of about 28° C. for duration of theassay. After 3 days, the numbers of live thrips were counted on eachpetal. The percent mortality was recorded 72 hours after treatment.

In this test, bilobalide, ginkgolide A, ginkgolide B, ginkgolide C andginkgolide J at 500 ppm showed at least 75% mortality in comparison withuntreated controls.

B.3 Brown Stink Bug (Euschistus heros)

The active compound is dissolved at the desired concentration in amixture of 1:1 (vol:vol) distilled water:acetone.

Fresh bean pods were placed in a transparent plastic cup and inoculatedwith ten adult stage individuals. Insects, food and inside of containerare sprayed with 1 ml solution using an air brush. Treated cups werekept at about 25° C. Percent mortality was recorded after 5 days.

In this test, bilobalide at 100 ppm showed at least 75% mortality incomparison with untreated controls.

B.4 Forest shield bug (Eysarcoris aeneus)

The active compound is dissolved at the desired concentration in amixture of 1:1 (vol:vol) distilled water:acetone.

Row peanuts and soybean seeds were placed in a plastic cup andinoculated with ten adult stage individuals. Insects, food and inside ofcontainer are sprayed with 1 ml solution using an air brush. Afterdrying, a water supply source will be placed in the cup and the cupclosed with a screened lid. Treated cups were kept at about 20° C.Percent mortality was recorded after 5 days.

In this test, bilobalide at 100 ppm showed at least 75% mortality incomparison with untreated controls.

B.5 Rice Leaf Bug (Trigonotylus caelestialium)

The active compound is dissolved at the desired concentration in amixture of 1:1 (vol:vol) distilled water: acetone.

Small wheat seedlings in glass tubes were sprayed with 200microliter/tube by air brush. After drying, ten 2nd and 3rd nymph stageindividuals were released in the tube and the tube closed with ascreened lid. Treated cups were kept at about 20° C. Percent mortalitywas recorded after 5 days.

In this test, bilobalide, and ginkgolide A at 100 ppm showed at least75% mortality in comparison with untreated controls.

B.6 Brown Stink Bug (Euschistus heros)

The active compound is dissolved at the desired concentration in amixture of 1:1 (vol:vol) distilled water: acetone.

Soybean seedlings of Intacta and BMX-Potencia with one pair of trueleaves were sprayed with 2 ml solution using an airbrush. After dry, theplants in small pots were placed inside a transparent plastic cage andinfested with 10 adults adult stage individuals. Treated cups were keptat about 25° C. Percent mortality was recorded after 1, 2, and 6 daysafter application.

In this test, bilobalide at 10 ppm and ginkgolide A at 100 ppm showedthe following mortality:

INTACTA dose mortality (%) mortality (Abbott %)* Product ppm a.i 1 D.A.A2 DAA 6 DAA 1 D.A.A 2 DAA 6 DAA Untreated — 5.0 5.0 20.0 — — —Ginkgolide A 100 12.5 20.0 62.5 7.9 15.8 53.1 Bilobalide  10 7.5 20.072.5 2.6 15.8 65.6

BMX — POTENCIA dose mortalty ppm mortality (%) (Abbott %)* Product a.i 1D.A.A 2 DAA 6 DAA 1 D.A.A 2 DAA 6 DAA Un- — 2.5 5.0 20.0 — — — treatedGink- 100 10.0 10.0 57.5 7.7 5.3 46.9 golide A Bilo- 10 5.0 7.5 60.0 2.62.6 50.0 balide DAA = Days After Application *Corrected mortalityaccording to Abbott, W.S., A method of computing the effectiveness of aninsecticide, J. Econ. Entonnal., 18 (1925) 265-267. The test shows thatbilobalide and ginkgolide A have a higher efficacy when applied tosoybean plants containing a toxin trait of Bacillus thuringiensis(INTACTA) than when applied to genetically modified soybean plantswithout the Bacillus thuringiensis trait (BMX- POTENCIA). This issurprising since the values in the untreated groups (corrected accordingto Abbott) are equal, i.e. the Bacillus thuringiensis toxin alone doesnot control brown stink bugs.B.7 Green Soldier Stink Bug (Nezara viridula)

Lima Bean (Phaseolus lunatus, ‘Henderson Bush,’ Lot #—VR06650) plantswere transplanted at the two true-leaf stage into 25.8 cm² pots filledwith sifted (No. 10 sieve) North Carolina loamy sand soil. Pots wereheld in the greenhouse and watered daily until treatment. Three daysafter transplant, the compounds were dissolved in acetone and thendiluted with water for a final concentration of 50% acetone. Treatmentswere applied as a drench in 1 ml solution per plant. Plants were held inan environmental chamber (25±2° C., 24 L) and watered as needed for theduration of the test.

Three days after treatment, plants were infested with five 2^(nd) instarnymphs. Plants were covered with organza fabric bags to prevent escape.Four days after infestation, the number of live nymphs on each plant wasrecorded, and means were calculated for each treatment. The percentcontrol was calculated as the percent mortality relative to the solventblank.

In this test, bilobalide, and ginkgolide A at 300 g ai/ha showed atleast 75% mortality in comparison with untreated controls.

B.8 Green Soldier Stink Bug (Nezara viridula)

Pots (25.8 cm²) were filled with a 1:1 mixture of sifted (No. 10 sieve)North Carolina loamy sand soil and play sand. Technical material wasdissolved in DMSO in a 20 ml scintillation vial. A total applicationvolume of 25 μl of solution was added to a 20 ml vial, ten lima beanseeds (P. lunatus) were added, and the vial was vortexed for 1 minute.Seeds were allowed to dry and planted at a depth of 2 cm later the sameday. One seed was planted per pot. Pots were held in the greenhouse andwatered daily until infestation.

Ten days after treatment, plants were infested with five 2^(nd) instarnymphs. Plants were covered with organza fabric bags to prevent escape.Plants were held in an environmental chamber (25±2° C., 24 L) andwatered as needed.

Four days after infestation, the number of live nymphs on each plant wasrecorded, and means were calculated for each treatment. The percentcontrol was calculated as the percent mortality relative to the solventblank.

In this test, ginkgolide A at 0.063 mg ai/seed showed at least 75%mortality in comparison with untreated controls.

We claim:
 1. A method for controlling pests of genetically modifiedsoybean plants, comprising contacting the soybean plant, parts of it,its propagation material, the pests, their food supply, habitat orbreeding grounds with one or more components of the ginkgo tree selectedfrom the group consisting of bilobalide, ginkgolide A, ginkgolide B,ginkgolide C, ginkgolide J and ginkgolide M wherein the soybean plantshave at least one toxin of Bacillus thuringiensis formed in the plant;and wherein the pests are from the family of Pentatomidae and/orThripidae.
 2. The method of claim 1, wherein the pests are Acrosternumspp., Euschistus spp., Nezara spp. and/or Piezodrus spp.
 3. The methodof claim 1, wherein the pests are Acrosternum hilare, Euschistus heros,Nezara viridula and/or Piezodrus guildini.
 4. The method of claim 1,wherein the component or components of the ginkgo tree are applied in anamount of from 1 to 500 g/ha.
 5. The method of claim 1, wherein thecomponents of the ginkgo tree are applied by foliar application.
 6. Themethod of claim 1 for protecting plant propagation material.
 7. Themethod of claim 1, wherein the components of the ginkgo tree are appliedto soybean plants that have at least one gene selected from CrylA(a),CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb andCrylF, or a combination thereof.
 8. The method of claim 1, wherein thepests are resistant to one or more of the insecticides selected from thegroup consisting of pyrethroids, neonicotinoids, and organophosphates.9. The method of claim 1, wherein the pests are selected fromdichromothrips sp.
 10. The method of claim 1, wherein the soybean planthas an increased tolerance to certain herbicidally active compounds.